EP0729934A2 - Verfahren zur Herstellung von 3-Alkoxy-2-substituierter Benzoesäure oder deren Ester - Google Patents

Verfahren zur Herstellung von 3-Alkoxy-2-substituierter Benzoesäure oder deren Ester Download PDF

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Publication number
EP0729934A2
EP0729934A2 EP96106726A EP96106726A EP0729934A2 EP 0729934 A2 EP0729934 A2 EP 0729934A2 EP 96106726 A EP96106726 A EP 96106726A EP 96106726 A EP96106726 A EP 96106726A EP 0729934 A2 EP0729934 A2 EP 0729934A2
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EP
European Patent Office
Prior art keywords
tert
butylhydrazine
methoxy
methylbenzoyl
chloro
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP96106726A
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English (en)
French (fr)
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EP0729934A3 (de
Inventor
Zev Lidert
Robert Eugene Hormann
Dat Phat Le
Thomas Ranson Opie
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Rohm and Haas Co
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Rohm and Haas Co
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Priority claimed from US07/984,189 external-priority patent/US5344958A/en
Application filed by Rohm and Haas Co filed Critical Rohm and Haas Co
Publication of EP0729934A2 publication Critical patent/EP0729934A2/de
Publication of EP0729934A3 publication Critical patent/EP0729934A3/de
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A01N43/30—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3 with two oxygen atoms in positions 1,3, condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/32—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C243/00—Compounds containing chains of nitrogen atoms singly-bound to each other, e.g. hydrazines, triazanes
    • C07C243/24—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids
    • C07C243/38—Hydrazines having nitrogen atoms of hydrazine groups acylated by carboxylic acids with acylating carboxyl groups bound to carbon atoms of six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/72—Hydrazones
    • C07C251/86—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to carbon atoms of six-membered aromatic rings
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    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
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    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/28—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups having nitrogen atoms of urea groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
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    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/50—Compounds containing any of the groups, X being a hetero atom, Y being any atom
    • C07C311/51—Y being a hydrogen or a carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/46—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms
    • C07C323/48—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having at least one of the nitrogen atoms, not being part of nitro or nitroso groups, further bound to other hetero atoms to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/38—Amides of thiocarboxylic acids
    • C07C327/56—Amides of thiocarboxylic acids having nitrogen atoms of thiocarboxamide groups further bound to another hetero atom
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/86—Hydrazides; Thio or imino analogues thereof
    • C07D213/87—Hydrazides; Thio or imino analogues thereof in position 3
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    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/24—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/58—One oxygen atom, e.g. butenolide
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    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
    • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
    • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
    • C07D317/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
    • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07C2601/14—The ring being saturated
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    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • the present invention is concerned with N'-substituted-N,N'-diacylhydrazines which are useful as insecticides, compositions containing those compounds and methods of their use.
  • the present invention is also concerned with the production of intermediates useful in the production of such compounds.
  • Prior processes for the production of the 3-alkoxy-2-alkylbenzoic acid intermediates useful in the production of some of the N'-substituted-N,N'-diacylhydrazines of the present invention have the production of 3-hydroxy-2-alkylbenzoic acid compounds from hydrochloride salt of 2-alkyl-3-aminobenzoic acid as a preceding step.
  • Such exothermic anilinium hydrochloride salt reactions pose reaction safety and substance stability concerns and require controlled cooling. Such constraints can create safety and cost burdens on the production of the useful intermediates concerned herein.
  • the present invention provides improved N'-substituted-N,N'-diacylhydrazines which are unexpectedly propertied with enhanced, higher activity as well as a safened method for production of intermediates useful for their production.
  • the combination of higher activity, better economics of manufacture, and safer production methods can provide an economic and environmental advantage in the use of the inventive compounds.
  • insecticidal compounds having the formula N-(2-R a -3-R b -4-R h -benzoyl)-N'-(2-R c -3-R d -4-R e -5-R f -benzoyl)-N'-R g -hydrazine which may be depicted structurally as follows: wherein R a is a halo or lower alkyl; R b is lower alkoxy, optionally substituted with halo (preferably fluoro); R c is selected from hydrogen, halo, lower alkyl, lower alkoxy, lower alkoxy lower alkyl, and nitro; R d , R e and R f are each independently selected from hydrogen, bromo, chloro, fluoro, lower alkyl, lower alkoxy, and lower alkoxy lower alkyl; R g is a (C 4 -C 6 )alkyl, e.g.
  • R h is hydrogen, lower alkoxy, lower alkyl, or when taken together with R b is methylenedioxy (-OCH 2 O-), 1,2-ethylenedioxy (-OCH 2 CH 2 O-), 1,2-ethyleneoxy (-CH 2 CH 2 O-) or 1,3-propyleneoxy (-CH 2 CH 2 CH 2 O-) wherein an oxo atom is located at the R b position; and the substituents R c and R d , or R d and R e , or R e and R f when taken together can be methylenedioxy or 1,2-ethylenedioxy.
  • compositions comprising an agronomically acceptable carrier and an insecticidally effective amount of such compounds; compositions comprising an insecticidally effective amount of such compounds and a surfactant; and methods of using such compounds and compositions, for example, methods for controlling insects such as insects of the order of Lepidoptera and Homoptera , which comprises contacting the insects with a compound or composition according to the present invention.
  • the compounds and compositions of the present invention are insecticidally active against insects of the order Lepidoptera . Certain of these compounds and compositions are distinguished by their insecticidal activity against insects of both the orders Lepidoptera and Homoptera .
  • Such methods may comprise effectively admixing a 3-amino-2-(substituted)benzoic acid, sodium nitrite and an alcohol under acidic conditions to produce a reaction mass predominantly comprising a 3-alkoxy-2-(substituted)benzoic acid.
  • the method comprises effectively admixing a 3,4-fused heterocyclic benzoic acid and an alkyl lithium reagent followed by subsequent reaction with an electrophilic reagent.
  • One embodiment of the present invention is an insecticidal compound having a formula of N-(2-R a -3-R b -4-R h -benzoyl)-N'-(2-R c -3-R d -4-R e -5-R f -benzoyl)-N'-R g -hydrazine, wherein R a is a halo, preferably bromo or chloro, or lower alkyl, preferably a (C 1 -C 3 )alkyl, more preferably methyl or ethyl; R b is lower alkoxy, preferably a (C 1 -C 4 )alkoxy, more preferably methoxy, trifluoromethoxy or ethoxy, most preferably methoxy or ethoxy; R c is selected from hydrogen, bromo, chloro, fluoro, lower alkyl (preferably a (C 1 -C 3 )alkyl, more preferably methyl), lower alk
  • Preferred insecticidal compounds include those wherein R b is methoxy and R h is hydrogen or when R b and R h taken together are methylenedioxy or 1,2-ethylenedioxy, and R g is tert -butyl. More preferred are those wherein R a is methyl, ethyl, chloro or bromo, R b is methoxy and R h is hydrogen or when R b and R h taken together are methylenedioxy or 1,2-ethylenedioxy, R g is tert -butyl, and wherein no more than three of R c , R d , R e and R f are the same member selected from a group consisting of bromo, fluoro and chloro or no more than two of R d , R e and R f are methoxy.
  • R c , R d , R e , and R f are the same member selected from bromo, chloro, fluoro, and methyl, or no more than two of R d , R e , and R f are methoxy.
  • the more preferred compounds are those wherein no more than three of R c , R d , R e and R f are independently selected from bromo, chloro, fluoro (preferably chloro, fluoro), methyl and methoxy with the remaining R c , R d , R e and R f being hydrogen.
  • R d and R f are independently selected from chloro, bromo, fluoro (preferably chloro), methyl and methoxy and R c and R e are both hydrogen, for example, (i) R d and R f are each independently selected from bromo, chloro, and fluoro, and preferably are each chloro, (ii) R d and R f are each independently selected from methyl and methoxy, and preferably are each methyl, or (iii) R d is selected from bromo, chloro, and fluoro, and R f is selected from methyl and methoxy, and preferably R d is chloro and R f is methyl.
  • Preferred insecticidal compounds of the present invention also include those comprising one or more of the following:
  • Preferred compounds because of their higher activity and/or better economics of production include:
  • Preferred insecticidal compounds wherein R g is (C 5 -C 6 )alkyl are those wherein R g is neopentyl or substituted neopentyl, preferably unsubstituted neopentyl, or methylneopentyl.
  • Preferred neopentyl compounds are N-(3-methoxy-2-methylbenzoyl)-N'-(3,5-dimethylbenzoyl)-N'-neopentylhydrazine, N-(3-methoxy-2-methylbenzoyl)-N'-(3,5-dimethylbenzoyl)-N'-(methylneopentyl)hydrazine, N-(3-methoxy-2-ethylbenzoyl)-N'-(3,5-dimethylbenzoyl)-N'-neopentylhydrazine and N-(3-methoxy-2-ethylbenzoyl)-N'-(3,5-dimethylbenzoyl)-N'-(methylneopentyl)hydrazine
  • More preferred compounds and compositions thereof because of their superior insecticidal activity against insects of the order Lepidoptera include:
  • More preferred compounds and compositions thereof because of their superior insecticidal activity against insects of the order Homoptera include:
  • the method can be performed by a process comprising effectively admixing a 3-amino-2-(substituted)benzoic acid or an ester thereof, sodium nitrite and an alcohol, preferably methanol or ethanol, or a mixture of water and an alcohol, preferably only an alcohol, under acidic conditions to produce a reaction mass comprising a 3-alkoxy-2-(substituted)benzoic acid or ester thereof, preferably 3-methoxy-2-(substituted)benzoic acid or 3-ethoxy-2-(substituted)benzoic acid.
  • the alcohol is methanol and a 3-methoxy-2-(substituted)benzoic acid is produced.
  • one process embodiment of the present invention is a process comprising admixing
  • the alcohol may, for example, be methanol or ethanol and a 3-alkoxy-2-(substituted)benzoic acid is produced.
  • the alcohol is methanol and a 3-methoxy-2-(substituted)benzoic acid, more preferably 3-methoxy-2-methylbenzoic acid or 2-ethyl-3-methoxybenzoic acid is produced.
  • R 2 , R 4 , R 5 , and R 6 independently can be hydrogen, a straight or branched (C 1 -C 10 )alkyl, a straight or branched halo(C 1 -C 10 )alkyl, a straight or branched (C 1 -C 10 )alkoxy, a straight or branched halo(C 1 -C 10 )alkoxy, or a halo substituent.
  • R 2 is a substituent consistent with the desired compound substitution.
  • Preferred 3-amino-2-(substituted)benzoic acids are 3-amino-2-methylbenzoic acid and 3-amino-2-ethylbenzoic acid.
  • halo substituents are are bromo, chloro, and fluoro.
  • a preferred halo(C 1 -C 10 )alkyl is trifluoromethyl.
  • R 3 is an alkyl moiety, preferably lower alkyl and more preferably methyl or ethyl, which results from the use of an alcohol in the process having the formula R 3 OH.
  • R 7 can be hydrogen, a straight or branched (C 1 -C 10 )alkyl, or a straight or branched halo(C 1 -C 10 )alkyl.
  • a straight or branched (C 1 -C 10 )alkyl can be n -butyl as a straight C 4 alkyl and sec -butyl or isobutyl as a branched C 4 alkyl.
  • the halogenated alkyls can be halogenated with one or more of the same or different halogen.
  • R 7 is a hydrogen or a (C 1 -C 4 )alkyl, more preferably hydrogen.
  • the acidic condition can be created by use of hydrobromic, hydrochloric, phosphoric, or sulfuric acid; preferably sulfuric acid.
  • the amount of the acid is that effective amount in combination with the utilized water or methanol to produce the desired alkoxylated product in substantial amounts.
  • the amount of acid can range from about 0.5 to about 5 mole equivalents, preferably from about 1 to about 4 mole equivalents, more preferably from about 1.5 to about 2.5 mole equivalents.
  • the amount of alkoxylated product produced in the reaction mass is preferably at least about sixty (60) per cent by weight, more preferably at least about eighty (80) per cent.
  • the reaction mass can comprise additional products consisting of hydroxylated products (e.g., "phenolic compounds") which have hydroxyl (OH) moieties at the 3 position (e.g., 3-hydroxy-2-methylbenzoic acid).
  • hydroxylated products e.g., "phenolic compounds” which have hydroxyl (OH) moieties at the 3 position (e.g., 3-hydroxy-2-methylbenzoic acid).
  • the hydroxylated by-product content of the reaction mass is less than ten (10) per cent by weight, more preferably less than about five (5) per cent by weight, and most preferably essentially an absence of the hydroxylated by-product.
  • the reaction mass also can comprise additional products which have replacement moieties bonded to the "oxy" oxygen of the carboxylic group of the 3-aminobenzoic acid [e.g., -CO 2 H --> -CO 2 R 3 ], wherein R 3 can be the alkyl portion of the alcohol used, e.g. methyl.
  • the reaction temperature can be room temperature up to the boiling temperature of the reaction mixture, although cooling can be done but is not required.
  • the temperature is from about 0°C to about 100°C, more preferably from about 25°C to about 75°C, most preferably from about 45°C to about 65°C.
  • an optional method of additional steps to convert any phenolic by-product produced in the reaction comprises subsequently admixing the reaction mass formed containing such phenolic compounds with
  • the amount of the base used can be preferably about 4 to about 6 equivalents and the amount of the methylating agent used can be preferably about 2 to about 4 equivalents.
  • the method can be performed by a process comprising effectively of mixing a 3,4-fused heterocyclic benzoic acid with an alkyl lithium reagent (e.g.
  • this method permits direct ortho-lithiation of certain benzoic acid derivatives in the presence of a carboxy group and obviates the need for other activating/protecting groups in place of the carboxy group.
  • a second process embodiment of the present invention is a process comprising admixing at a temperature of from about -90 °C to about -20 °C for from about one to about four hours
  • R 8 and R 9 independently may be hydrogen, a straight or branched (C 1 -C 10 )alkyl, or a or straight or branched (C 1 -C 10 )alkoxy.
  • R 8 and R 9 are hydrogen.
  • X may be methylene (CH 2 ), oxy (O), thio (S) or N-R 12 , where R 12 may be a straight or branched (C 1 -C 10 )alkyl.
  • Y may be oxy, thio or N when N forms a double bond with an adjacent carbon atom.
  • X is O or CH 2 and Y is O.
  • the methylene chain length represented by n may be 1-3, preferably 1 or 2.
  • the 3,4-fused heterocyclic benzoic acid is a 3,4-methylenedioxybenzoic acid, a 3,4-(1,2-ethylenedioxy)benzoic acid, a 3,4-(1,3-propylenedioxy)benzoic acid, a 3,4-(1,2-ethyleneoxy)benzoic acid, or a 3,4-(1,3-propyleneoxy)benzoic acid.
  • the 3,4-fused heterocyclic benzoic acid may be 2-methyl-3,4-methylenedioxybenzoic acid, 2-ethyl-3,4-methylenedioxybenzoic acid, 3,4-(1,2-ethylenedioxy)-2-methylbenzoic acid, 2-ethyl-3,4-(1,2-ethylenedioxy)benzoic acid, 2-methyl-3,4-(1,2-ethyleneoxy)benzoic acid, 2-ethyl-3,4-(1,2-ethyleneoxy)benzoic acid, 2-methyl-3,4-(1,3-propyleneoxy)benzoic acid or 2-ethyl-3,4-(1,3-propyleneoxy)benzoic acid.
  • the lithiating reagent R 10 Li may be n -butyl lithium, sec -butyl lithium, tert -butyl lithium, or phenyl lithium, preferably n -butyl lithium.
  • the aprotic reaction solvent may be tetrahydrofuran, ethyl ether, 1,4-dioxane, hexanes, or mixtures of these.
  • the preferred solvent is tetrahydrofuran.
  • the reaction mixture may also contain adjunctive lithium chelators such as tetramethylethylenediamine (TMEDA).
  • TMEDA tetramethylethylenediamine
  • the electrophilic reagent is represented by the formula R 11 Z wherein R 11 is lower alkyl, preferably methyl or ethyl, perhaloalkyl, or is a halo such as chloro, bromo or iodo, and Z is a halo such as chloro, bromo or iodo, an alkylcarbonyl such as acetyl or propionyl, an alkylcarbonyloxy such as acetoxy, or formyl. More preferably, the electrophile is a lower alkyl iodide, such as methyl or ethyl iodide.
  • the reaction temperature for ortho-lithiation can be from about -90° to about -20° C, preferably from about -50° to about -80° C.
  • the reaction time for ortho-lithiation may be about 1-4 hours, preferably about 2 hours.
  • the reaction temperature for reaction of the electrophilic reagent can be from about -90 °C to about room temperature.
  • the electrophilic reagent is added at about -65 °C and the reaction mixture is permitted to warm to about room temperature without additional heating.
  • the reaction time for reaction of the electrophilic reagent can be from about 30 minutes to about 2 hours.
  • the agronomically acceptable salts of the present insecticidal compounds can be synthesized by the utilization of the salting methods known in the art relating to N'-substituted-N,N'-diacylhydrazines used as insecticides.
  • the compounds of the present invention exhibit unexpectedly excellent results in their use as insecticides.
  • One skilled in the art will be able to determine the activity of a given compound against a given insect and the dosage required to obtain unexpectedly good insecticidal effects.
  • the exact dosage for a given situation can be routinely determined and the compositions and formulations for such uses, and the desired additional components (such as agronomically acceptable carriers, diluents, extenders and other common additives used in insecticidal compositions) can be determined in the known manners.
  • another embodiment is an insecticidal composition
  • R a is a halo or lower alkyl
  • R b is lower alkoxy, optionally substituted with halo (preferably fluoro)
  • R c is selected from hydrogen, halo (e.g.
  • R d , R e and R f are each independently selected from hydrogen, bromo, chloro, fluoro, lower alkyl, lower alkoxy, and lower alkoxy lower alkyl;
  • R g is a (C 4 -C 6 )alkyl;
  • R h is hydrogen, lower alkoxy, lower alkyl,or when taken together with R b is methylenedioxy(-OCH 2 O-), 1,2-ethylenedioxy (-OCH 2 CH 2 O-), 1,2-ethyleneoxy (-CH 2 CH 2 O-) or 1,3-propyleneoxy (-CH 2 CH 2 CH 2 O-) wherein an oxo atom is located at the R b position; and the substituents R c and R d , or R d and R e , or R e and R f when taken together can be methylenedioxy or 1,2-ethylened
  • Also embodied is a method for controlling insects comprising contacting the insect with an insecticidally effective amount of a compound having the formula N-(2-R a -3-R b -4-R h -benzoyl)-N'-(2-R c -3-R d -4-R e -5-R f -benzoyl)-N'-R g -hydrazine wherein R a is a halo or lower alkyl; R b is lower alkoxy, optionally substituted with halo (preferably fluoro); R c is selected from hydrogen, halo (e.g.
  • R d , R e and R f are each independently selected from hydrogen, bromo, chloro, fluoro, lower alkyl, lower alkoxy, and lower alkoxy lower alkyl;
  • R g is a (C 4 -C 6 )alkyl;
  • R h is hydrogen, lower alkoxy, lower alkyl, or when taken together with R b is methylenedioxy (-OCH 2 O-), 1,2-ethylenedioxy (-OCH 2 CH 2 O-), 1,2-ethyleneoxy (-CH 2 CH 2 O-) or 1,3-propyleneoxy (-CH 2 CH 2 CH 2 O-) wherein an oxo atom is located at the R b position; and the substituents R c and R d , or R d and R e , or R e and R f when taken together can be methylenedioxy or 1,2-ethylenedi
  • a preferred method is a method wherein R a is methyl, ethyl, chloro or bromo, R b is methoxy and R h is hydrogen or when R b and R h taken together are methylenedioxy or 1,2-ethylenedioxy, R g is tert -butyl, and wherein no more than three of R c , R d , R e and R f are the same member selected from a group consisting of bromo, fluoro and chloro or no more than two of R d , R e and R f are methoxy.
  • EXAMPLE 7 Preparation of N-(3-methoxy-2-methylbenzoyl)-N'-(3,5-dimethylbenzoyl)-N'- tert -butylhydrazine from Products of EXAMPLES 4 and 6
  • reaction mixture was allowed to reach room temperature and stirred continuously for 1 additional hour, whereupon the reaction mixture was diluted with methylene chloride (12 L), washed with water, dried over magnesium sulfate, filtered and stripped to give N-(3-methoxy-2-methylbenzoyl)-N'-(3,5-dimethylbenzoyl)-N'- tert -butylhydrazine (663 g), melting at 204-204.5 °C.
  • a 250 mL round-bottom flask equipped with a nitrogen purge, septum inlet, and magnetic stirring was dried under a nitrogen atmosphere and charged with 2.5 g (15 mmoles) of piperonylic acid and 100 mL of tetrahydrofuran.
  • the solution was cooled to -70 °C, and n -butyl lithium (1.6 M, 22 mL, 35.2 mmoles) was added.
  • the mixture was stirred for 2 hours at -70 °C.
  • Methyl iodide (3 mL, 48.2 mmoles) was added at ⁇ -65 °C, the mixture was stirred for 1 hour at -70 °C, and the solution was then allowed to warm to 0 °C.
  • 1,4-Benzodioxan-6-carboxaldehyde (8.87 g, 54 mmoles), 19.68 g methanol, 50.3 wt % sodium hydroxide (5.99 g) and 30 % aqueous hydrogen peroxide (5.30 g, 46.8 mmoles) were heated in a 250 mL flask for 17 minutes at 39-52 o C and 18 minutes at 52-58 o C oil bath temperature. After the moderate foaming had subsided, 30 % aqueous hydrogen peroxide (13.54 g, 119 mmoles) was added in three roughly equal portions over 22 minutes at 58-66 o C.
  • n -butyl lithium solution (total 35 mL) was added in five increments at -70 to -61 o C. These additions dissolved most of the fine solid that precipitated when the original solution was cooled. Six minutes later, 16.3 g tetrahydrofuran was added in an attempt to dissolve the remainder of the solid. The suspension was stirred for a total of 4.2 hours at -63 to - 72 o C after the final n -butyl lithium addition. Then 99 % iodoethane (7.17 g, 46.0 mmoles) was added at -65 o C, giving only a slight exotherm.
  • the aqueous layer and wash were acidified and extracted with hexanes/diethyl ether to give crude product containing (by gas chromatography) 61 area % starting acid and 26 % of the desired 5-ethyl-1,4-dioxan-6-carboxylic acid.
  • the crude product in about 14 g of diethyl ether/hexanes was purified by eight stages of partial neutralization/extraction into dilute aqueous sodium hydroxide (the ethylated acid preferentially remained in the organic layers) to give 5-ethyl-1,4-benzodioxan-6-carboxylic acid (0.54 g).
  • the gas chromatographic analysis showed about 88% purity with a melting point of 148-176 o C.
  • the proton NMR spectrum indicated a 92/8 weight ratio of ethylated and unethylated 1,4-benzodioxan-6-carboxylic acid.
  • test solution containing 600 parts per million (ppm) was made by dissolving a compound of this invention in a 1:1 acetone:methanol solution, then adding water to give a 5:5:90 acetone:methanol:water solution, and finally a surfactant was added at an equivalent of 28.4g (1 ounce) of surfactant per 378,5 L (100 gallons) of test solution. Serial dilutions were prepared in water from the 600 ppm solution.
  • Foliar insecticidal evaluations were made on one or both of the following pests: the Southern Armyworm (SAW), Spodoptera eridania , and the Potato Leafhopper (PLH), Empoasca fabae .
  • SAW Southern Armyworm
  • PHL Potato Leafhopper
  • the PLH (3 Day) column heading is the observed percentage mortality for the Potato Leafhopper when treated with a compound of the present invention at a concentration of 10 ppm.
  • Celite is a trademark of Celite Corporation which may be registered in one or more of the designated states.

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EP96106726A 1992-11-23 1993-11-08 Verfahren zur Herstellung von 3-Alkoxy-2-substituierter Benzoesäure oder deren Ester Withdrawn EP0729934A3 (de)

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US07/984,189 US5344958A (en) 1992-11-23 1992-11-23 Insecticidal N'-substituted-N,N'-diacylhydrazines
US984189 1992-11-23
US08/129,549 US5530028A (en) 1992-11-23 1993-09-29 Insecticidal N'-substituted-N,N'-diacylhydrazines
US129549 1993-09-29
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Families Citing this family (62)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013836A (en) * 1992-02-28 2000-01-11 Rohm And Haas Company Insecticidal N'-substituted-N,N'-disubstitutedhydrazines
US5369127A (en) * 1993-04-21 1994-11-29 Allergan, Inc. 1,3-benzodioxole and 1,2-dialkoxybenzene derivatives as ocular hypotensive agents
US5948406A (en) * 1996-08-12 1999-09-07 Rohm And Haas Company Immunogens, antibodies formed therefrom, and coating antigens useful in a diacylhydrazine immunoassay method
US5917079A (en) * 1996-09-24 1999-06-29 Rohm And Haas Company Process for synthesizing benzoic acids
DE19730848A1 (de) 1997-07-18 1999-01-21 Bayer Ag Verfahren zur Herstellung von 3-Hydroxy-2-methylbenzoesäure
US6013671A (en) * 1998-02-03 2000-01-11 Rohm And Haas Company Synergistic insecticidal compositions
US6124500A (en) * 1998-03-09 2000-09-26 Rohm And Haas Company Process for synthesizing benzoic acids
US6258603B1 (en) * 1998-06-17 2001-07-10 Rohm And Haas Company Ligands for modulating the expression of exogenous genes via an ecdysone receptor complex
DE19831710A1 (de) * 1998-07-15 2000-01-20 Merck Patent Gmbh Diacylhydrazinderivate
IL133121A (en) 1998-12-08 2004-06-20 Dow Agrosciences Llc Process for making 2-alkyl-3-hydroxybenzoic acids
US20040033600A1 (en) * 2001-03-21 2004-02-19 Palli Subba Reddy Ecdysone receptor-based inducible gene expression system
US8105825B2 (en) 2000-10-03 2012-01-31 Intrexon Corporation Multiple inducible gene regulation system
US6576422B1 (en) 2000-10-17 2003-06-10 Rohm And Haas Company Method for identifying products employing gene expression
WO2002066615A2 (en) 2001-02-20 2002-08-29 Rheogene, Inc. Novel substitution mutant receptors and their use in a nuclear receptor-based inducible gene expression system
WO2002066613A2 (en) 2001-02-20 2002-08-29 Rheogene Holdings, Inc Novel ecdysone receptor/invertebrate retinoid x receptor-based inducible gene expression system
DK1373470T3 (da) 2001-02-20 2013-07-29 Intrexon Corp Hidtil ukendte substitutionsmutantreceptorer og deres anvendelse i et cellekernereceptorbaseret inducerbart genekspressionssystem
ES2392508T3 (es) * 2001-02-20 2012-12-11 Intrexon Corporation Receptores X retinoides quiméricos y su uso en un sistema inducible de expresión génica basado en receptores de ecdisona novedoso
WO2003030125A1 (de) * 2001-09-25 2003-04-10 Werner Keber Verfahren und einrichtung zum verhindern einer unzulässiggen flugannäherung von flugzeugen an zu schützende bodenobjekte
MXPA04002810A (es) * 2001-09-26 2005-06-06 Rheogene Holdings Inc Acidos nucleicos receptores de ecdisona de saltarilla, polipeptidos, y sus usos.
CA2820170C (en) 2001-09-26 2016-07-05 Intrexon Corporation Whitefly ecdysone receptor nucleic acids, polypeptides, and uses thereof
US7375093B2 (en) 2002-07-05 2008-05-20 Intrexon Corporation Ketone ligands for modulating the expression of exogenous genes via an ecdysone receptor complex
US7304161B2 (en) 2003-02-10 2007-12-04 Intrexon Corporation Diaclhydrazine ligands for modulating the expression of exogenous genes in mammalian systems via an ecdysone receptor complex
US7304162B2 (en) * 2003-02-21 2007-12-04 Intrexon Corporation Oxadiazoline ligands for modulating the expression of exogenous genes via an ecdysone receptor complex
US7456315B2 (en) 2003-02-28 2008-11-25 Intrexon Corporation Bioavailable diacylhydrazine ligands for modulating the expression of exogenous genes via an ecdysone receptor complex
US7935510B2 (en) 2004-04-30 2011-05-03 Intrexon Corporation Mutant receptors and their use in a nuclear receptor-based inducible gene expression system
US20070212716A1 (en) * 2006-02-10 2007-09-13 Commonwealth Scientific & Industrial Research Org. Nezara viridula Ecdysone Receptor
JP5881291B2 (ja) 2007-05-29 2016-03-09 イントレキソン コーポレーション エクジソン受容体複合体を通して外因性遺伝子の発現を調節するためのキラルジアシルヒドラジンリガンド
AU2008289461A1 (en) 2007-08-23 2009-02-26 Intrexon Corporation Methods and compositions for diagnosing disease
WO2009039001A1 (en) * 2007-09-17 2009-03-26 Rohm And Haas Company Compositions and methods for the modification of physiological responses in plants
EP2205249B1 (de) 2007-09-28 2018-11-07 Intrexon Corporation Therapeutische genschalterkonstrukte und bioreaktoren zur expression biotherapeutischer moleküle und ihre verwendung
MX2010003720A (es) * 2007-10-08 2010-10-20 Intrexon Corp Celulas dendriticas creadas por ingenieria genetica y usos para el tratamiento de cancer.
CN103038343A (zh) 2010-03-23 2013-04-10 英特瑞克斯顿股份有限公司 条件表达治疗蛋白的载体，包含所述载体的宿主细胞，及其应用
SG192856A1 (en) 2011-03-04 2013-09-30 Intrexon Corp Vectors conditionally expressing protein
TWI586640B (zh) 2011-09-08 2017-06-11 英翠克頌公司 結晶狀二醯基肼及其用途
CN103563953A (zh) * 2012-08-05 2014-02-12 南京华洲药业有限公司 一种含甲氧虫酰肼和氟啶脲的复合杀虫组合物及其用途
CN102863355B (zh) * 2012-09-24 2014-05-21 浙江禾田化工有限公司 一种n-(3-甲氧基-2-甲基苯甲酰基)-n’-叔丁基肼的提纯方法
CN102960356A (zh) * 2012-12-12 2013-03-13 海利尔药业集团股份有限公司 一种含有双三氟虫脲与甲氧虫酰肼的杀虫组合物
CN103416409A (zh) * 2012-12-15 2013-12-04 海利尔药业集团股份有限公司 一种含有氟螨嗪与甲氧虫酰肼的杀虫组合物
US9127024B2 (en) 2013-03-15 2015-09-08 Intrexon Corporation Boron-containing diacylhydrazines
CN103222466A (zh) * 2013-04-26 2013-07-31 南通金陵农化有限公司 一种吡蚜酮和甲氧虫酰肼的复配农药
CN104072383A (zh) * 2014-07-10 2014-10-01 四川北方红光特种化工有限公司 制备3-氨基-2-甲基苯甲酸的方法
CN107406373B (zh) 2014-09-17 2020-04-28 英特瑞克斯顿股份有限公司 含硼的二酰基肼化合物
WO2016116445A1 (en) * 2015-01-23 2016-07-28 Syngenta Participations Ag Pesticidally active semi-carbazones and thiosemicarbazones derivatives
SG11201802912PA (en) 2015-10-10 2018-05-30 Intrexon Corp Improved therapeutic control of proteolytically sensitive, destabilized forms of interleukin-12
JP6976244B2 (ja) 2015-11-11 2021-12-08 プレシゲン，インコーポレイテッド 心臓状態および他の病態の処置のための複数の生物学的に活性なポリペプチドを単一のベクターから発現させるための組成物および方法
UY37343A (es) 2016-07-25 2018-02-28 Intrexon Corp Control del fenotipo en plantas
AU2017359342B2 (en) 2016-11-09 2022-02-17 Intrexon Corporation Frataxin expression constructs
AU2018207281B2 (en) 2017-01-10 2024-08-01 Precigen, Inc. Modulating expression of polypeptides via new gene switch expression systems
CN108530297B (zh) * 2017-03-03 2021-09-24 联化科技股份有限公司 2-氯-3-甲基苯甲酸及其中间体的制备方法
CN109384667A (zh) * 2017-08-02 2019-02-26 江苏永安化工有限公司 一种2-甲基-3-甲氧基苯甲酰氯的合成工艺
SG11202008508QA (en) 2018-03-06 2020-10-29 Precigen Inc Hepatitis b vaccines and uses of the same
CN112088015A (zh) 2018-03-06 2020-12-15 普莱西根股份有限公司 人乳头瘤病毒疫苗及其用途
CN109776464A (zh) * 2019-03-26 2019-05-21 江苏省农药研究所股份有限公司 呋喃虫酰肼的制备方法、中间体及其制备方法
WO2020206056A1 (en) 2019-04-04 2020-10-08 Greenvenus Llc Peptides and methods of plant protection
CN113121339B (zh) * 2021-04-19 2022-10-11 江苏永安化工有限公司 一种3-羟基-2-甲基苯甲酸甲酯与3-甲氧基-2-甲基苯甲酸甲酯的联产工艺
CN113511968A (zh) * 2021-04-19 2021-10-19 江苏永安化工有限公司 一种2-甲基-3-甲氧基苯甲酸的合成工艺
BR112023023835A2 (pt) 2021-05-14 2024-01-30 Syngenta Crop Protection Ag Composições para tratamento de sementes
WO2022268815A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag Insect, acarina and nematode pest control
WO2022268813A1 (en) 2021-06-24 2022-12-29 Syngenta Crop Protection Ag Insect, acarina and nematode pest control
GB2612942A (en) * 2021-09-16 2023-05-24 Rotam Agrochem Int Co Ltd A crystalline form of methoxyfenozide, a process for its preparation and use of the same
WO2023105064A1 (en) 2021-12-10 2023-06-15 Syngenta Crop Protection Ag Insect, acarina and nematode pest control
CN117654560B (zh) * 2023-12-01 2024-06-04 安徽泽升科技股份有限公司 一种通过氧化氨基连续化制备硝基化合物的方法

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4161611A (en) * 1976-02-23 1979-07-17 Veesicol Chemical Corporation Process for the production of 2-methoxy-3,6-dichlorobenzoic acid
US4389401A (en) * 1979-07-10 1983-06-21 Rohm And Haas Company Arthropod repellents
DK483586A (da) * 1985-10-21 1987-04-22 Rohm & Haas Insecticide n'-substituerede-n,n'-diacylhydraziner
US5117057A (en) * 1985-10-21 1992-05-26 Rohm And Haas Company Insecticidal N' substituted-N-N'-disubstituted-hydrazines
US4985461A (en) * 1985-10-21 1991-01-15 Rohm And Haas Company Insecticidal N'-substituted-N,N'-diacylhydrazines
US5110986A (en) * 1988-04-26 1992-05-05 Rohm And Haas Company Synthesis of n-t-alkyl-1,2-diacylhydrazines
JPH0660142B2 (ja) * 1989-06-02 1994-08-10 田辺製薬株式会社 ビフェニル誘導体、その製法及びその合成中間体
ZA894508B (en) * 1988-06-16 1990-03-28 Rohm & Haas Pharmaceutical compounds
US4954655A (en) * 1989-03-31 1990-09-04 Rohm And Haas Company Preparation of alkylhydrazines
NZ228936A (en) * 1989-05-01 1992-04-28 Rohm & Haas Method for treating insect infestation in rice plants comprising applying diacylhydrazine derivatives
JPH0539252A (ja) * 1990-08-01 1993-02-19 Nippon Kayaku Co Ltd Ｎ，Ｎ’−ジベンゾイル−ｔｅｒｔ−ブチルヒドラジン誘導体およびそれを有効成分とする殺虫組成物
JP3068846B2 (ja) * 1990-08-01 2000-07-24 日本化薬株式会社 新規ヒドラジン誘導体およびそれを有効成分とする殺虫組成物
US5110979A (en) * 1991-01-15 1992-05-05 Imperial Chemical Industries Plc Trisubstituted benzoic acid intermediates
IL100643A (en) * 1991-01-25 1996-10-31 Nippon Kayaku Kk History of hydrazine and pesticides containing these histories as an active ingredient
US5334753A (en) * 1992-03-12 1994-08-02 Rhone-Poulenc Agriculture Ltd Processes for preparing ortho-substituted benzoic acids

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CA2103110C (en) 2004-09-14
EP0729934A3 (de) 1997-02-26
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KR100317793B1 (ko) 2002-11-27
NZ250170A (en) 1997-08-22
EP0602794A3 (de) 1994-11-30
PH31254A (en) 1998-06-18
US5530028A (en) 1996-06-25
CN1116271C (zh) 2003-07-30
CN1038673C (zh) 1998-06-10
HRP931427A2 (en) 1996-06-30
IL107533A (en) 1999-01-26
ATE179166T1 (de) 1999-05-15
CN1088572A (zh) 1994-06-29
GR3030029T3 (en) 1999-07-30
EP0602794B1 (de) 1999-04-21
CA2103110A1 (en) 1994-05-24
HUT75039A (en) 1997-03-28
MY111887A (en) 2001-02-28
EP0729953A2 (de) 1996-09-04
CN1182075A (zh) 1998-05-20
ES2130232T3 (es) 1999-07-01
AU5063593A (en) 1994-06-02
BR9304789A (pt) 1994-07-05
AU683224B2 (en) 1997-11-06
NZ280487A (en) 1998-02-26
IL107533A0 (en) 1994-02-27
KR940011414A (ko) 1994-06-21
DE69324552T2 (de) 1999-12-23
DK0602794T3 (da) 1999-10-25
DE69324552D1 (de) 1999-05-27
EP0729953A3 (de) 1997-02-26
CN1067050C (zh) 2001-06-13
CN1176251A (zh) 1998-03-18
CN1176245A (zh) 1998-03-18
BG98232A (en) 1995-02-28
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CN1072217C (zh) 2001-10-03

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